CorrosionControlEbook

ADVANCES IN
CORROSION CONTROL
COATING TECHNOLOGY
A JPCL eBook
iStockphoto/curraheeshutter
i
Advances in
corrosion control
coating technology
A JPCL eBook
Copyright 2011 - 2015 by

Technology Publishing Company
2100 Wharton Street, Suite 310
Pittsburgh, PA 15203
All Rights Reserved
This eBook may not be copied or redistributed

without the written permission of the publisher.
2011-2015 Technology Publishing Co.

SPONSORED BY
Contents ii

FEVE RESIN
Contents
iv Introduction
1
FEVE Technology for Higher Performance Coating Systems on Bridges
Bob Parker, AGC Chemicals Americas
Titans of the Abyss: Polyurethane, Polyurea, and Hybrid Lining
6 Technology
Mike ODonoghue Ph.D. and Vijay Datta MS, International Paint LLC
19
Paint & CoatingsWhere Are We Now?
Brian Goldie, JPCL
24
Improving Polyurethane Pipe Coatings for Harsh Conditions
Andreas aus der Wieschen, Matthias Wintermantel, Todd Williams and Ahren
Olson, Bayer MaterialScience AG
Raw Material Suppliers Answer Calls for Green and Smart Coatings
30 Brian Goldie, JPCL

Introduction iv
Introduction
This eBook features articles from the Journal of Protective Coat-
ings & Linings (JPCL) about technological advancements in
heavy-duty coatings for corrosion control.
iStockphoto/Bim

FEVE
Technology 1
FEVE Technology for

Higher Performance Coating
By Bob Parker,
AGC Chemicals Americas Systems on Bridges
T he history of coating system types used on steel bridges has always paralleled the evolution
of coatings technology as a whole. When breakthroughs have occurred, the bridge coating
market has paid attention and embraced these advancements. Sometimes, regulations have
played a significant part in altering this course of evolution, but the goal of the stewards responsible for
bridge maintenance and preservation has never changed. The ideal coating system will always be the
one that offers the best protection of the substrate at a reasonable cost, with due respect for compli-
ance with regulations.
The most popular long-life coating system in place at this time for bridges with challenging applica-
tions and environments is a three-coat system consisting of a zinc-rich primer, an epoxy midcoat and a
polyurethane topcoat. Other less expensive coating systems still exist, but many provide lesser protec-
tion and have a shorter lifetime. Depending on the available funding for any specific bridge project,
these options may be the only choice. However, if the goal of the bridge steward is the ultimate protec-
tion of the bridge against structural degradation for the longest period of time, the standard three-coat
system is the preferred choice.
Fluoroethylene vinyl ether (FEVE) fluoropolymer technology has proven to be a successful addition
to the global bridge coating market (Fig. 1). In the U.S., there is a growing interest from state DOTs,
Fig. 1: The Swan Bridge in Muroran,

Japan, is one of many bridges worldwide
that has seen a longer life cycle thanks to
its FEVE resin-based topcoat.
All photos and figures courtesy of AGC
Chemicals Americas, Inc.

2
local municipalities and the private sector

(Fig. 2). The discussion of the life cycle of a
coating system has paved the way for this
growing interest, as the cost of coating a
bridge decreases dramatically when it is
based on the lifetime of the coating system.
When the life cycle costs of bridge painting
and maintenance are taken into account,
then the use of fluoroploymer coatings be-
comes cost effective.
This article will discuss the chemistry be-
hind FEVE technology, coating types that
can be formulated with FEVE resins, and
Fig. 2: FEVE resin-based coatings are becoming more widely accepted for bridges in the U.S., including the the performance of FEVE-based coatings
Gateway Bridge in Nashville, Tenn.
used as topcoats on steel bridges.
FEVE Resin Structure

FEVE technology is most effective when incorporated into the aforemen-
tioned three-coat system. The FEVE polyol resins play an integral part in
the topcoat layer, replacing the standard acrylic or polyester polyols as
Fig. 3: This graphic illustrates the structure of the FEVE resin backbone. The the principle binder. This technology has been commercial since 1982
fluorinated segments (blue) provide weatherability and chemical resistance;
the vinyl ether segments (green) provide gloss, solubility and crosslinking and has been used on bridge coating systems across the globe since its
properties; and the R groups provide OH functionality, flexibility introduction. The key performance improvements of the FEVE polyol
and adhesion.
resins over traditional polyesters are their resistance against UV degra-
dation and their resistance to moisture permeation. The structure of the
resins backbone is illustrated in Figure 3.
The uniqueness of this resin lies in the combination of fluoropolymer chemistry with vinyl ether chem-
istry, allowing both chemistries to bring their respective strengths to the polymers performance. With-
out the presence of fluorine, the polyol would lack its superior weatherability and resistance properties.
Without the vinyl ether, the common properties of most organic resins solubility in solvents, available
functional groups, and adjustability of the glass transition temperature (Tg) would be absent and the
resin could not function in liquid coatings.
Coating Formulations with FEVE Resins

As with any coating, the performance of the finished product is dependent on many factors. Each raw
material plays a part in either improving or weakening the coatings performance. When an FEVE
polyol is part of a formulation, it can only benefit from the careful choice of other components in the for-
mulation. The whole concept of creating a coating that will endure for many years necessitates consid-
eration of every ingredient in the coating to be the best choice for weatherability and resistance
properties. There can be no weak link in the chain.
Several types of coatings can be produced with FEVE resin technology. The original coating in
1982 was a solvent-based, two-component finish that used an aliphatic polyisocyanate as the
cross-linker. It strongly resembled conventional polyurethane finishes in curing behavior and
methods of application. This system cures and applies just like a conventional polyurethane fin-
ish, but with far superior exterior durability. This coating type is still the fluorinated topcoat of
choice on bridges. VOC regulations in certain regions of the U.S. have made reformulation nec-
essary, but the availability of solid FEVE resins and their ability to dissolve in VOC-exempt sol-

3
vents have preserved the presence of this

technology to date.
In 2012, a water-based FEVE polyol disper-
sion entered the coatings market. This resin uti-
lizes water-emulsifiable aliphatic polyisocyanates
as its cross-linking partner. Up to now, water-
based, two-component polyurethane technology
has not been widely accepted in the bridge coat-
ing market, due to the increased sensitivity to at-
mospheric conditions like temperature and
humidity when these coatings are applied. Con-
sequently, this resin has only been tested in labo-
ratory trials. To date, the advantages of FEVE
Fig. 4: This graph compares two different FEVE resin-based coatings against two other popular bridge top-
coats. The coatings were tested inside of a QUV weatherometer for 3,000 hours, and the two FEVE-based water-based resin chemistry are only being real-
coatings showed significantly better gloss retention percentages than the other coatings tested. ized in factory-applied finishes for prefabricated
bridge components, where the reduction in VOCs
will improve the air quality of the interior working
space.
A third FEVE resin type, a water-based emul-
sion synthesized to a high molecular weight, is
available for use in one-component coatings for
bridges. Several DOTs across the country have
incorporated one-component, water-based coat-
ings, which are predominantly acrylic-based. Ex-
tensive lab work has been completed in the
testing of topcoats that contain FEVE emulsions.
Due to the strict limitations in cost dictated by the
current price range of the acrylic-based coatings
that have penetrated this market, most of the
Fig. 5: This graph compares the gloss retention of a FEVE resin-based coating against a PVDF polyurethane FEVE emulsion-containing formulations use both
coating and a standard acrylic-urethane bridge topcoat. As the exposure to UV light increased, the FEVE FEVE emulsions and acrylic emulsions as the
coating again displayed the best gloss retention percentage. binder portion. Performance improvement has
been evident in formulations utilizing 20 to 50 per-
Table 1: Results of FEVE Topcoat
Application on Tokiwa Bridge cent FEVE emulsion as the binder, depending on the particular color.
Initial Final Gloss Color It is prudent to mention the mechanism by which FEVE resins resist degradation by UV
60 Gloss 60 Gloss Retention (%) Change ( ) E radiation. FEVE resins do not absorb the suns UV radiation. Without absorption, no exci-
75 69 91 3.5 tation of the FEVE chemical bonds can occur, and the resin basically remains unchanged.
This is the key to the superior durability of FEVE resins. Accordingly, since they do not ab-
sorb the light, they cannot block it either. This is an important point to consider when formulating a
FEVE-based coating. UV absorbing and light stabilizing additives must be formulated into FEVE
resin-based clear coatings to protect any base coating to which it is applied. The most popular addi-
tives are the organic UV absorbers and hindered amine light stabilizers available on the market. To
expand on this any pigmented FEVE resin-based formulation will also be improved with the use of
UV light-stabilizing additives. These additives can extend the lightfastness of pigments, which al-
lows coatings systems to remain robust against UV degradation.

4
Performance Properties
Both accelerated exposure testing and real-life exposure testing have been per-
formed on coatings using FEVE technology. Figures 4 (p. 40) and 5 show com-
parisons of FEVE resin-based coatings with different coatings also used as
topcoats for bridge coating systems.
The graph in Figure 4 shows two different FEVE resin-based coatings a
100% FEVE polyol, and a 78% FEVE polyol blended with 22% polyester polyol.
FEVE solvent-based resins, like the FEVE emulsions, have a wide range of com-
patibility with other polyols. Laboratory work is being done to measure the per-
formance capabilities of these blended formulations. Some physical properties of
the paint film, such as flexibility, can be improved when non-FEVE polyols be-
come part of the formulation. As this graph shows little change with the 60-de-
gree gloss at 3,000 hours, the exposure is still in progress.
The second test exposure was done at the Equatorial Mount with Mirrors for
Acceleration with Water (EMMAQUA) test site in Arizona (Fig. 5). The meas-
urement of UV exposure is in megajoules per square meter (MJ/m2). Again,
the FEVE coating showed the best gloss retention percentage of all the coat-
ings tested.
Certain bridge applications are being monitored for their performance. The
The Tokiwa bridge is located in Japan (Fig. 6). This bridge was recoated in
1986, using two coats of an epoxy primer and two coats of a FEVE-based top-
coat. The changes in 60-degree gloss and color over 25 years of exposure are
shown in Table 1 (p. 3).
Additional Considerations
Because the main function of FEVE resin-based coatings is to extend the life of
the coating system, it is important to point out other proposals for bridge coating
longevity that should to be considered in order to achieve this goal. Some
thought has been given to expanding the procedure for coating a bridge so that
the critical components of the bridge get the best protection from the coating sys-
tem. Conversely, the remaining components, which are not prone to early coating
failure, can be given a lesser degree of protection. This idea is explained in detail
in a JPCL article written in 1984 by Clive Hare, entitled Specific Utility In the De-
sign of Coating Systems for Steel Bridges. Hare states that, The ever-increas-
ing demands on bridge paint systems (fed by increasing traffic loadings, salt
usage, and years of neglect) must be met by the use of heavier duty coating sys-
Fig. 6: These photos show the Tokiwa Bridge in Japan, which was tems applied with great exactitude over better surfaces.
coated with a FEVE-based topcoat in 1986. The photo on the top
The article goes into detail about specific areas of bridges that have historically
was taken in 1988, the middle photo in 1993, and the photo on
the bottom in 2014. Clearly, there has been very little change in experienced premature coating failure resulting in damaging corrosion of the
the coating's gloss and appearance over the years. steel. The seams, edges, bolts and rivets of bridges are most susceptible (Fig. 7).
These are the areas that need coating systems that are more functional for corro-
sion resistance. In many instances, these areas do not receive the level of UV radiation experi-
enced by other parts of the bridge, but the need for recoating is still critical.
The use of a FEVE resin-based topcoat has demonstrated the ability to resist the penetration
of chloride ions through energy-dispersive X-ray microanalysis testing. However, the difficulty of
attaining success lies in the morphology of certain bridge components and the challenge of
coating application on these components. Although FEVE technology can offer greater

5
longevity of the topcoat on a bridge, the protection of every steel surface, for up to thirty years,
is still a significant challenge.
Conclusion
Although FEVE technology has shown itself as a viable alternative to standard topcoats for the
three-coat system for bridges, research is continuing on the utilization of this technology in
combination with zinc-rich primers or epoxy primers to create an effective two-coat system.
The elimination of an entire coat will significantly lower the final cost of the coating project.
As the evolution of coatings for bridges continues, the ultimate goal will always be the most
Fig. 7: Certain bridge components such as efficient protection of the steel substrate at the most reasonable cost. If we can succeed in pro-
seams, edges, bolts and rivets still present
coating and life cycle challenges, even for
longing the life of an important part of our nations infrastructure, much will be gained from this
FEVE-based coatings. success.
About the Author

Bob Parker is a technical service chemist for AGC Chemicals Americas in Exton, Pa. He has been
involved in formulating paints and coatings for over 30 years. He received his Bachelor of Science
degree in chemistry from Alvernia College. He is currently responsible for technical service for
LUMIFLON fluoropolymer resins in the U.S.
JPCL

Lining
Technology 6
Titans of the Abyss:

By Mike ODonoghue Ph.D. Polyurethane, Polyurea, and
and Vijay Datta MS
International Paint LLC Hybrid Lining Technology
T he demand for enhanced productivity, cost reduction, fast throughput, and optimization of
life cycle costs associated with high-performance lining applications is often met using
two-component, solvent-free polyurethane, polyurea, and polyurethane/polyurea hybrids.1-3
Moreover, these thermoset technologies can readily comply with todays stringent environmental regu-
lations, as exemplified by their low- or zero-VOC content and absence of oxygen-depleting substances
(ODSs).
The genesis of polyurethanes hails back to the pioneering work on isocyanates by Otto Bayer in
1937. As a result of Bayers work, thin-film polyurethane finish coats later became for decades the de
facto finish coat of choice on structural steel. It was not until the early 1980s when thick-film and single-
coat solvent-free aromatic polyurethane linings were formulated
for use on girth welds, valves, and pipe. By the mid-1980s, ad-
vanced versions of these polyurethane linings were being used on
large-scale pipe rehabilitation projects in Western Canada.4 Then,
by the late 1980s, an innovative generic class of thick-film and sin-
gle-coat solvent-free coatings and linings emerged on the
scenepolyureas.57 Like their fast-reacting and fast-curing
polyurethane predecessors, the even faster gel time and cure time
of the polyureas necessitated that these linings be applied by plu-
ral-component spray equipment.
In the early 1990s, further advances led to new and improved
polyurethane and polyurea linings in which properties could be
customized. Later, various hybrids of both technologies were de-
veloped and touted by some to have a combination of the best
properties of multiple technologies.8 Interestingly, many of todays
so-called polyurethanes are actually hybrids, and the implied ter-
minology distinctions among polyurethane, polyurea, and
polyurethane/polyurea hybrid descriptions has become somewhat
blurred.9 For example, a coating may be described as a
polyurethane, but it is actually a hybrid.
This article will focus primarily on very fast-cure, solvent-free
polyurethanes, polyureas, and polyurethane/polyurea hybrid tech-
nologies, many of which are well-suited to immersion service: the
veritable Titans of the Abyss.
The chemistry, cure mechanism, safety aspects, strengths, and
weaknesses of each technology will be discussed. Case histories
will be provided for each technology.
In todays fast-track lining projects, the gel time and cure time of
a given lining might vary from a few seconds to a few hours. Coat-
istockphoto.com/whitphotography 2011-2015 Technology Publishing Co.

7
ing formulators and polymer chemists can utilize these technologies to carefully tailor elas-
tomeric or high-tensile strength rigid linings for specific tank and pipe internals or externals.
Depending on the chemistry of a polyurethane, polyurea, or hybrid, the applications for
these linings are diverse.
Examples of applications include the following:
penstocks, riveted and welded;
potable water processing, transportation, and storage;
aquariums;
pipelines exposed to raw sewage and erosion degradation;
Fig. 1: Polyurethane formation
concrete digesters;
cooling water intakes;
primary and secondary containment;
rail cars;
oilfield pipelines;
icebreakers (underwater hulls);
platforms;
barges;
syntactic foams for sub-sea projects;
and
Fig. 2: Polyurea formation
food storage.
Each service represents conditions in which one or more factors, such as corrosion and
erosion resistance, flexibility, immersion resistance, and wear resistance are important. All three lining
technologies have been used on carbon steel, galvanized steel, ductile iron, and concrete substrates.
Lining Selection: The Influence of Chemistry in Polyurethane, Polyurea, and Hybrids

Common to the polyurethane, polyurea, and hybrid linings is the use of an isocyanate component in the
cure reaction.10
Essentially, the film formation of a polyurethane lining stems from the reaction of isocyanate groups (-
NCO) with hydroxyl groups (-OH moieties) in a polyol (Fig. 1). At least one catalyst is normally used to
improve the reaction of the isocyanate and hydroxyl groups.
In contrast, in the film formation of a polyurea lining, the isocyanate groups react with an amine group
(e.g., -NH2). A catalyst is not used in this reaction (Fig. 2).
Case History: Paper Mill Wastewater Treatment Clarifier, U.S.

In 1996, a newsprint mill in the U.S. discovered that the concrete structures of its wastewater
clarifier, particularly the walls, were experiencing extensive corrosive attack from hydrosul-
furous acid, sulphuric acid, and hydrogen sulphide.21
The corrosion had resulted in exposed rebar, and aggregate protruded up to a half-inch in
certain areas. Approximately 10,000 square feet required refurbishment.
Within 72 hours, the concrete walls and steel center (including rakes) were abrasive blasted
and respectively lined with 125 mils DFT and 60 mils DFT of a 100%-solids polyurethane lin-
ing.
Polyurethane lining in paper mill After five years, the clarifier was drained, and the linings were inspected. The linings were
wastewater treatment clarifier21 found to be completely intact on the entire 10,000 square feet of surface (See photo above
(concrete substrate)
and on p. 48).
The rapid productivity associated with this one-coat lining installation, coupled with the out-
standing performance in immersion, was lauded by the owner of the facility.

8
As expected by the term hybrid, in the film formation of a hybrid lining,

both the isocyanate-polyol and isocyanate-amine reactions occur. The re-
action rate and concentration of urethane or urea linkages depend on the
proportion of polyurethane to polyurea in a given hybrid formulation as
well as the usual consideration of stereochemistry of the reaction part-
ners and number of reactive groups. As with polyurethanes, a catalyst is
Fig. 3: Formation of carbamic acid invariably used to control the reaction with hybrids.11
Because the reaction rates of water and isocyanates and of polyols and
isocyanates are typically within an order of magnitude of one another, it is
critical to ensure that water does not contact the isocyanate in a
polyurethane lining application. Should water contact the isocyanate, a
cross-interference reaction will take place and the polyurethane structure
will be compromised. An unstable carbamate will form and decompose to
carbon dioxide and an amine (Fig. 3). By way of comparison, the reaction
rates of water and isocyanates are many orders of magnitude less than
the reaction rates of amines and isocyanates; thus, polyurea and hybrid
applications are far less sensitive to moisture.5
The chemical, mechanical, and thermal properties of each of these lin-
ings depend on the chemical makeup of the raw materials, the type and
strength of the chemical bonds, the spatial configuration and steric hin-
drance of organic substituents on certain atoms, the resultant molecular
linkages in the polymer film, and the ultimate ingenuity of the lining for-
mulator.
Fig. 4: Structures of various polyols Although performance in various services can vary markedly, these lin-
ings, as a whole, have excellent barrier properties and interpose a high
electrical resistance into a corrosion cell circuit.
Definitions
In terms of chemistry and cure mechanism, a more thorough definition of polyurethane, polyurea, and
hybrid technology is available from the Polyurea Development Association.12
Polyurethane: For reference purposes, a polyurethane coating/elastomer is that derived from the
reaction product of an isocyanate component and a resin blend component. The isocyanate can be
aromatic or aliphatic in nature. It can be a monomer, polymer, or any variant reaction of isocyanates,
quasi-prepolymer, or a prepolymer. The prepolymer, or quasi-prepolymer, will be made from hydroxyl-
terminated polymer resins.
The resin blend must be made up of hydroxyl-terminated polymer resins, being diol-, triol-, or multi-
hydroxyl polyols, and/or aromatic or aliphatic hydroxyl-terminated chain extenders. The resin blend
may also contain additives, or non-primary components. The resin blend will contain catalyst(s) for sys-
tem reactivity.
Polyurea: A polyurea coating/elastomer is that derived from the reaction product of an isocyanate
component (as described for a polyurethane) and a resin blend component. The isocyanate can be
aromatic or aliphatic in nature.
The resin blend must be made up of amine-terminated polymer resins, and/or amine-terminated chain
extenders. The amine-terminated polymer resins will not have any intentional hydroxyl moieties. Any hy-
droxyls are the result of incomplete conversion to the amine-terminated polymer resins. The resin blend
may also contain additives, or non-primary components. These additives may contain hydroxyls, such as
pre-dispersed pigments in a polyol carrier. Normally, the resin blend will not contain a catalyst(s).

9
Table 1: Reactions of the Isocyanate Group2 Hybrid: For reference purposes, a

polyurethane/polyurea hybrid coating/elastomer
Hydrogen Donor General Reaction Product Class is the reaction product of an isocyanate compo-
Structure Product Structure
nent (as above) and a resin blend component.
Water H2O + RNCO Amines + RNH2 + H2O
The resin blend may be made up of blends of
carbon dioxide (RNHCONNR)
(leading to amine-terminated and/or hydroxyl-terminated
disubstituted urea) polymer resins, and/or amine-terminated and/or
Hydroxyl groups R OH
1
+ RNCO Urethanes RNHCOOR 1
hydroxyl-terminated chain extenders. The resin
Amine groups R1NH2 + RNCO Disubstituted RNHCONHR1 blend must contain blends of amine-terminated
ureas and hydroxyl-terminated moieties. The resin
Disubstituted R1NHCONHR2 + RNCO Substituted R1NHCONR2CONHR3 blend may also contain additives, or non-primary
ureas biurets
components. The resin blend may contain cata-
Urethane R1NHCOOR2 + RNCO Allophonates R1NHCOHR2COOR2
lyst(s) for system reactivity.
Carboxylic acids R1COOH + RNCO Amides RNHCOR1
Table 1 shows the reactions of the isocyanate
group with various hydrogen donating groups
Isocyanates will also react well with the following less common hydrogen donors.
and the resulting structures obtained.2
Imino groups - NH Sulfonamide groups - SO2NH2

Polyurethanes: Film Formation
Substituted amine groups - NHR Sulfonamides - SO2NHR
Figure 4 (p. 45) shows structures of polyether
Carbonamide groups - CONH2 Thioamide groups - SHNR2
and polyester polyols. Some of these polyols
Substituted carbonamides - CONHR Sulphonic acid groups - SO2OH
may be used to react with an isocyanate compo-
Sulfhydryls - R1SH
nent such as straight methylene diisocyanate
(MDI) or a quasi-prepolymer derived from MDI it-
self. Figure 5 (p. 48) shows a typical structure of an isocyanate component used in
the film formation of a solvent-free, single-coat aromatic polyurethane lining.
Figure 6 (p. 48) is an oversimplified representation of the micro-structures of
polyurethane elastomers and the high-tensile strength, rigid, and hard
polyurethane linings. In the polymer network, the polyurethane exhibits a two-
phase morphology consisting of soft and hard segments.13 The soft segment is be-
Fig. 5: Structure of isocoyanates
(example: MDI methylene diphenylisocyanate) cause of the long-chain, high-molecular weight polyether or polyester polyols,
which are relatively non-polar, whereas hard segments consist of the diisocyanate
and short-chain, low-molecular weight chain extender(s), which are relatively polar.
The chemical stability and physical characteristics of a polyurethane film are de-
rived from the chemistry of the individual components. Generally, polyester-based
polyurethanes are more resistant to oil, grease, solvents, water, UV, ozone, and
wear, whereas polyether polyurethanes are more resistant to hydrolysis, low tem-
perature flexing, and microbes/fungus. Tailoring the chemical resistance and physi-
cal properties of a given polyurethane system can be accomplished by adjusting
the ratio of hard and soft segments and the amount of chemical cross linking. In-
creasing the hard-segment concentration and cross linking of the system results in
harder polymers that are generally more chemically and hydrolytically stable than
soft polymers because the hard segment is hydrophobic and less rapidly at-
tacked.13,14 Conversely, a high soft-segment concentration and low cross link den-
sity will produce a softer, more elastic polyurethane.
When a polyurethane coating is engineered to be an under cross linked film
Fig. 6: Two-phase morphology:
hard and soft segments in polyurethanes (NCO:OH <1), the film typically will be more flexible and less resistant to solvent
and chemicals. In comparison, the same system formulated to produce an over

10
Disadvantages
Advantages of Polyurethane Linings of Polyurethane Linings
Rapid productivity in shop and field applications, e.g., pipelines Moisture sensitivitysusceptibility to
Elimination of solvents and compliance with stringent air pollution regulations (VOCs) thickening, gelation, and foaming
Single coat, high-build applications up to 250 mils (~6,000 microns) Relatively low alkali and solvent resistance
Formulated in a broad spectrum of cure timesminutes to hours Potential allergic reactions due to any
Rapid curing even at sub-zero temperatures free isocyanate content
Formulation diversity based on vast selection of polyol and isocyanate raw materials Susceptible to undercutting and peeling
when immersed linings are
Customized water and chemical resistance, flexibility, and impact resistance
mechanically damaged when not
Coated pipes are readily inspected and buried within minutes of application formulated properly for this service
Low surface frictionexcellent hydraulic characteristics for pipeline internals Poor cathodic disbondment resistance
Good cathodic disbondment resistance at temperatures below 50 C at temperatures above 50 C
Can be used with geotextiles Poor hot water adhesion
Abrasion resistance can be superior to AR steel Poor color retention in aromatic
Repairable by hand within minutes (kits available) polyurethanes with UV exposure
Polyurethane lining in paper mill wastewater treatment

clarifier21 (steel substrate)
cross linked film (NCO:OH >1) will yield a

harder and more chemical-resistant film.
Aromatic isocyanate groups are far more reac-
tive than aliphatic isocyanate groups in polyiso-
cyanates. Consequently, linings derived from
aromatic diisocyanates, for example, dry and
cure faster than comparable systems based on
aliphatic isocyanates. The high viscosity of the
Fig. 7: Structure of amine resin in a polyurea polyol and isocyanate components, in addition
to fast set times, necessitate the use of plural-
component spray equipment. (However, repair kits of polyurethane linings are available for use on
touch-up joints and connections).
A later development to thick-film aromatic polyurethane linings has been the advent of high-solids,
aliphatic polyurethane coatings.15 In essence, three approaches were used to commercialize high-per-
formance, solvent-free aliphatic polyurethane linings:
low molecular weight compounds with lower viscosity,
reactive diluents, and
new polyurethane prepolymers.
While aliphatic systems are of great interest, less expensive, higher performing aromatic

11
polyurethanes are used for immersion service.

In terms of rapid throughput of lined pipes, for example, in shop applications or pipe rehabilitation
projects, the fast-set and rapid-cure characteristics of polyurethane linings are highly advantageous,
saving both time and money. (Some advantages and disadvantages of polyurethane linings are listed
on p. 48).
Polyureas: Film Formation

Typical structures of amine resins are shown in Fig. 7. To form urea linkages, and thus polyurea linings,
extremely fast cross linking occurs through the isocyanate/amine-terminated resin (Fig. 2.) According
to the PDA, the resulting polymer is termed a pure polyurea.
Rapid set times of less than one minute and a cure reaction largely unaffected by atmospheric mois-
ture are features synonymous with two-component polyurea linings. Therefore, in terms of time, project
Polyurea lining in wastewater treatment costs, and overall productivity, the fast-set and rapid-cure characteristics of polyurea linings are highly
clarifier26 (concrete substrate)
advantageous, both in shop applications and field work where quick returns to service are critical.
Advantages of Polyurea Linings As with solvent-free polyurethane linings, in the

polymer network of a polyurea lining, there is two-
Rapid productivity in shop and field applications
phase morphology consisting of soft and hard seg-
Not sensitive to moisture ments. The isocyanate component is often a
Fast setting and faster cure than polyurethanes, e.g., in seconds quasi-prepolymer derived from MDI. Given that
Superior to polyurethanes with respect to application under high humidity polyurea, polyurethane, and hybrid coatings can
Customized water and chemical resistance, flexibility, and impact resistance have similar structural backbones, it is not surpris-
Low surface frictionexcellent hydraulic characteristics for pipeline internals ing that versions of each lining type can exhibit ei-
Low VOCcompliant with stringent air pollution regulations (VOCs) ther similar chemical resistance properties or
Can be applied at sub-zero temperatures remarkably different chemical resistance properties.
Good elongation/flexibility It cannot be overemphasized that applying
High thermal stability under dry conditions polyurea linings over damp surfaces or placing the
lining in service prematurely can lead to significant
loss of adhesion and early failure of the system.
Disadvantages of Polyurea Linings Because of the fast reactivity of the isocyanate-amine reaction, special spray application
Poorer wetting out of substrates, due equipment may be required that uses impingement mixing, i.e., the base and hardener compo-
partly to very rapid set times nents are mixed externally at the tip of the spray gun. Not surprisingly, this type of application
Potential allergic reactions due to any free invariably requires
isocyanate content a fairly precise matching of base and hardener viscosities;
Susceptible to undercutting and peeling heating the components; and
when immersed linings are mechanically ensuring the correct pressure at the tip. Otherwise, mixing is incomplete, and the chemical
damaged if not formulated properly for and physical properties of the polymer are compromised.16
this service The rapid curing characteristics of polyureas can lead to substrate adhesion difficulties be-
Can be difficult to touch up and repair cause of the limited time that is available for the films to wet the substrate. (Wetting provides
Poor hot water adhesion an intimate degree of contact between the rapidly gelling resin and the substrate.) The limited
Relatively low alkali and solvent resistance wetting time can cause difficulties when applying polyureas over concrete, especially if it has
Poor color retention in aromatic polyureas been abrasive blasted to remove the cohesively weak, cement-rich outer layer that has devel-
subject to UV exposur oped against the formwork. In areas where the polyurea needs to be terminated, some manu-
Limited raw material options compared to facturers require a set of sawcuts (often two) into the concrete parallel to the intended edge to
polyurethanes and polyurethane hybrids form a termination notch. These notches are typically about 56 mm wide by about 10 mm
Very fast cure properties reduce recoat deep and provide an additional physical anchor.
windows, thereby increasing the risk In addition, the fast reactivity makes touch-up and repair by brush application difficult on
of layering
small areas. Polyurea coatings must be spray-applied; therefore, tying-in to an existing

12
Advantages of Hybrid Linings coating is difficult. Some manufacturers make

special repair grades, but these are often
Rapid productivity in shop and field applications
heavily modified with diluent resins to achieve
Fast cure and fast return to immersion service within minutes of application
sufficient pot life and viscosity for brush appli-
Wider range for reaction time and performance properties
cation. Unfortunately, the modifications can
Caustic resistance: 50% at 65 Csuperior to polyurethane linings
drastically alter the repair-film properties, in-
Customized water and chemical resistance, flexibility and impact resistance cluding loss of mechanical and chemical resist-
Generally, good cathodic disbondment resistance at temperatures below 50 C ance.
Films are resistant to abrasion, erosion, and impact With a relatively large number of isocyanate
Films that are unaffected by normal shrinkage cracks in concrete and amine components to choose from, the
Low surface friction that enhance hydraulic characteristics for pipeline internals polyurea chemist can formulate elastomer
Repairable by hand within minutes (kits available). films with various cure speeds and with good
flexibility, elongation, and tensile strength prop-
Disadvantages of Hybrid Linings erties. Depending on the amine backbone, the
Susceptible to undercutting and peeling when immersed linings are mechanically films can be formulated with good water resist-
damaged if not formulated properly for this service ance properties for immersion service in the
Potential allergic reactions due to any free isocyanate content wastewater industry. However, the hydrocar-
Poor color retention with UV exposure in hybrids derived from aromatic isocyanates bon solvent resistance of polyurea linings (es-
pecially to aromatic solvents) is typically poor.
One of the very common challenges with
polyureas is their very short recoat windows due
to fast cure times. It is common for polyureas to
demonstrate layering and poor bonding between
coats because of the fast cure times.
As far as temperature resistance is con-
cerned, while the dry temperature resistance
of polyurea linings can be up to 150 C, even
the most thermally stable polyurea linings will
probably not survive hot aqueous immersion
environments above 50 C. For oilfield serv-
ices, pure polyurea products may have limited
use due to their poor resistance to polar sol-
vents.
Some of the advantages and disadvantages of
polyurea linings are summarized in the chart on
Polyurethane hybrid lining on steel internals of penstock8

p. 51.
Hybrids: Film Formation

Customized hybrid linings can be beneficial for owners and applicators. For instance, hybrid linings
can be formulated to exhibit significantly harder and better damage resistance than a typical
polyurea, while also retaining a linear and somewhat flexible polymeric structure. By virtue of their
outstanding barrier properties and elongation features, hybrid linings are well suited to protect the
internals of concrete digesters.
Hybrid polyurethane/polyurea linings can be formulated to have the best combination of proper-
ties of the two technologies.8 The hydrophobic character of some of the aromatic polyurethane-
polyurea hybrids is very similar to that of high-performance, immersion-grade epoxies. Hence, the
moisture vapor transmission of the hybrids is often below a measurable quantity when tested as per

13
Case History: Penstock Internals, Australia

Since the early 1990s, some polyurethane hybrids have been used to internally line penstocks in
North America.28 The rapid productivity associated with the use of these linings and their solvent-
free safety advantages made them particularly attractive for large scale penstock projects. These
one-coat polyurethane hybrids have had great success protecting thousands of rivet heads in im-
mersed conditions in penstocks.
Based on this success, in 2004, the internals of a penstock at a power station in Australia were
lined with a one-coat system of a solvent-free elastomeric polyurethane hybrid. Several hundred
meters of three- and four-foot internal diameter pipe were lined.
Polyurethane hybrid lining8 in a pen-
First, the carbon steel internals were abrasive blasted to SSPC-SP 10, Near White Metal, using
stock (steel substrate; robotic, self- a robot (a self-propelled, automatic blasting unit). Second, the polyurethane hybrid lining was ap-
propelled automatic blasting unit) plied at approximately 4060 mils DFT, as shown in photo at left.
After eight years, the penstock has shown no evidence of any lining problems.
Case History: Wastewater Treatment Clarifier, U.S.

The eight year old concrete walls and floor of a primary clarifier in a food processing plant had
sustained considerable damage by erosion and chemical attack from a solution of calcium sul-
phate. The owner was concerned that the concrete was in imminent danger of failure.
Given that an epoxy lining system had been used in the past and had failed in three years,
the owner elected to re-line and protect the 22,000 sq ft of damaged concrete with a propri-
etary polyurea lining system.
All concrete surfaces were abrasive blast cleaned, followed by a spray application of a spe-
cialty concrete primer.27
A spray applied topcoat of .080 inches polyurea was then applied.
Polyurea lining in wastewater treat-
ment clarifier26 (concrete substrate) The project was completed in 24 hours and re-watered in two hours (See photo at left and on
p. 50).
ASTM E96, Method B.

Hybrid linings have the ability to incorporate geotextile fabric, fiberglass reinforcement, woven
polypropylene, and polyester fabrics to produce a composite with improved properties. These in-
clude tear strength; crack-bridging capability; and the ability to cope with surface moisture and out-
gassing during application, and subsequent movement in a substrate such as concrete.
The longer wet time of the hybrid facilitates penetration into both the substrate and any internal
reinforcement being used, thereby improving wetting and offering superior mechanical adhesion.
With ultra fast-set coatings and linings such as polyureas, this type of mechanical adhesion is ex-
tremely difficult to achieve. On damp surfaces, the hybrid will still adhere to the substrate. Some
pin-holing can occur in the glue-coat due to outgassing. Outgassing will not affect the topcoat be-
cause the outgassing will dissipate in the geotextile. On the other hand, when a polyurea lining is
applied to a damp surface, it will cure very fast, so it is less likely to outgas. However, the polyurea
lining also will not adhere to the substrate.
Ultra-high-build aromatic polyurethane hybrids have been shown to possess exceptional resist-
ance to water and wastewater immersion services. Their tough, robust, and flexible films are similar
to some of the best high-tensile strength polyurethane films and have been used for more than 20
years in demanding immersion exposures where abrasion and impact are additional factors of con-
cern. Repair kits of hybrid linings are available for touch-up joints and connections.
Like polyurethane and polyurea linings, hybrids also have extremely fast return-to-service times

14
Table 2: General Comparison of Polyurethane, Polyurea, for ambient temperature water and wastewater
and Hybrid Properties in the Coatings and Linings Industry immersion service (domestic waste and indus-
trial waste at a pH from less than 1 to 14).
Property Polyurethane Polyurethane Polyurea Polyurethane Hybrid
Certain hybrid linings use hydroxyl- and
Hybrid Advantage
amine-containing resins that have very little to
Gel time Seconds Instant set Instant set Superior
to hours to minutes substrate wetting no oxygen atoms, or other atoms that would in-
crease polarity in the resin backbones. This
Tack free Minutes One minute 630 Rapid return
to hours to hours seconds to service chemical make up causes the hybrids to be
Tensile Up to Up to Up to Higher tensile much more hydrophobic than polyurethane
strength 7,000 psi 7,000 psi 4,000 psi strength and polyurea linings. The hybrids also resist
Tensile Up to 500% Up to 500% Up to 700% Lower elongations chemicals as much as, or better than, many
elongation however, significantly polyurethane and polyurea linings.
lower permeability
Shore 50A to 85D 5OA to 85D 50A TO 85D Harder, better General Discussion
hardness D impact resistance
Table 2 provides a general comparison of
Abrasion Pure As low as 76 mg loss Hybrids often
polyurethane, polyurea, and
resistance polyurethanes 30 mg (H18 wheel) have better
typically (H18 wheel) abrasion resistance polyurethane/polyurea hybrid properties in the
have best coatings and linings industries.
AR props A high degree of surface preparation must
Tear resistance Up to 500 pli Up to 500 pli Up to 500 pli Similar tear be done in order to ensure that the solvent-
resistance
free and high-build polyurethane, polyurea,
Moisture vapor Too low Too low 42 Significantly better
and hybrid linings will perform well for many
transmission to detect to detect g/m2/24hrs resistance to
the passage years and provide the owner with a good re-
of moisture turn on his investment. For optimum results,
steel surfaces should be free of surface con-
taminants such as soluble salts, grease, and oil; be abrasive blasted to a minimum SSPC-SP 10;
and have a deep and jagged profile of 35 mils (75125 microns).
By virtue of their short pot lives and fast curing properties, these linings are applied using plural-
component, hot airless spray equipment. Humidity control is important, and the surface temperature
should be at least 3 degrees C above the dew point.
One of the key areas where polyurethane and hybrid technology have demonstrated long-term
immersion performance has been in the lining of potable water tanks and pipes. Certified to the
ANSI/NSF 61 standard, these coatings have a long track record when applied to steel substrates.
The same is true for polyurethane coatings applied to the interior and exterior of steel per AWWA
C222-99. The rapid curing characteristics of this technology, coupled with the need to use special-
ized equipment, behooves owners to select qualified applicators and ensure that third-party inde-
pendent inspection is provided to ensure a successful application.
Lining and relining steel penstocks is another application where polyurethane and hybrid
polyurethanes excel.14,17 Of particular note is that a single-coat application of these films can provide
long-term corrosion protection to rivets in penstocks, some designed and installed in the 1940s.
Another immersion environment where polyurethane and hybrid polyurethane linings have been
used is the underwater hulls of ice breakers.18 The excellent abrasion resistance and low frictional
resistance indicate that these coatings would be well suited to resist abrasion and ice impact. While
these characteristics proved to be the case on many icebreakers, in more recent years, epoxy lin-
ings have become favored more than polyurethane and hybrid polyurethane linings for icebreaker
underwater hulls.

15
Table 3: Transmission Pipeline Coating Testing The low temperature cure of some
polyurethanes and hybrid urethanes is very
Solvent-Free Hybrid Polyurethane: Testing in Accordance with Qualification Protocol for Liq-
uid Epoxy Coatings useful in cold climates. In the Canadian oil
Test Test Method Test Results patch, for instance, where several fast-set
28 day cathodic disbondment @ 20C 35.9 mm epoxy coatings are used for transmission
28 day cathodic disbondment @ 65C CSA Z245.20-06 1.8 mm pipeline externals, some owners prefer the
28 day cathodic disbondment @ 80C Clause 12.8 0.6 mm
use of fast-set polyurethane linings. Judi-
ciously selected and qualified high-perfor-
28 day adhesion @ 65C CSA Z245.20-06 #2 ratings
28 day adhesion @ 80C Clause 12.14 #1 ratings mance polyurethanes and hybrids are well
suited to year-round rehabilitation of steel
1.5 J impact resistance @ -30C, -10C, 0C, CSA Z245.20-06 No holidays pipelines.19 It should be noted, however, that
23C, 65C and 75C Clause 12.12 the service temperature for suitable
1.5 flexibility @ 0C No cracks or
polyurethanes is invariably rated up to 65C,
1.5 flexibility @ -30C CSA Z245.20-06 stretch marks i.e., less than the temperature of alternative
2.5 flexibility @ 0C Clause 12.11 Cracking and qualified epoxy coatings with high glass tran-
2.5 flexibility @ 0C disbondment sition temperatures.
Considering accelerated laboratory testing,
Hardness (-30C, -10C, 0C and 23C) Shore D 80 to 85 the authors have stressed, in previous work,
the importance of not relying heavily on cer-
ASTM D2240
tain tests and understanding the relevance of
Hardness (65C and 80C) Shore D 57 to 68
said tests.20 For transmission pipeline coat-
Gouge Test NACE Draft 54.1% ings, caution must be exercised in not placing
too much credence in any individual pre-quali-
Electrochemical Impedance Spectroscopy ISO 16773 Log Z > 10 fication test. Therefore, testing programs for
(10.7 to 10.8)
epoxies, polyurethanes, and polyurethane hy-
brids typically consist of a regime that in-
cludes electrochemical impedance, cathodic disbondment resistance, wet adhesion, impact
resistance, flexibility, hardness, and gouge-resistance assessments.
Table 3 shows the pre-qualification test results for a thick film, solvent-free polyurethane hybrid
developed for use on a major oil companys transmission pipelines.21 The coatings wet adhesion
characteristics and its impact resistance were excellent, and it displayed good flexibility at the 1.5
degrees per pipe diameter bend, but displayed poor flexibility at a 2.5 degree bend. Gouge resist-
ance was rated at 54.1% (average gouge depth of total film thickness). The coating showed excel-
lent electrochemical impedance characteristics, with the log Z impedance remaining constant
during 28 days of exposure to the test conditions.
In the final analysis, all the test results were excellent, except for one anomalous result in the CD
test in accordance with CSA Z254-20-02. Outstanding cathodic disbondment resistance was exhib-
ited by the polyurethane lining at elevated temperatures. At 80C for 28 days, the average disbond-
ment radius was 0.6 mm; at 65C for 28 days, the average disbondment radius was 1.8 mm.
However, at 23C for 28 days, the average disbondment radius was 35.9 mm. At first glance, this re-
sult would disqualify the coating until the coating chemistry and the relevance of the test methodol-
ogy were considered in addition to other physical tests. The coating has a much higher tensile
strength (6,000 psi) and elasticity at ambient temperature when compared to its tensile adhesion
(3,500 psi). Therefore, in the CD test at 23 C, this polyurethane coating had a very high molecular
strength, but the coating would peel when pried off in the CSA test, thereby erroneously giving the
impression of poor adhesion. Elevating the test temperature to 65 C and 80 C progressively lowers
the tensile strength, and the coating subsequently becomes more difficult to pry from the substrate.
Hence, caution should be exercised in the disqualification criteria for a polyurethane (or polyurea

16
and polyurethane hybrid) coating based on ra-

dial disbondment measurements obtained
from CD tests.
Bonded Geomembrane Lining The immersion performance of the solvent-
free polyurethane, polyurea, and polyurethane
POLYURETHANE HYBRID BASECOAT hybrid linings is a function of their chemistries
POLYURETHANE HYBRID TOPCOAT Outgassing and the nature of their dry and wet adhesion
(air & water vapor) at the polymer-substrate interface. Micro im-
purities (e.g., micronic backside contamina-
GEOTEXTILE FABRIC
tion) embedded in surface irregularities and
Hydrostatic adsorbed layers of gaseous or liquid phase
Infiltration molecules are more likely to be problematic
EPOXY PRIMER (Optional) for the application of extremely fast-set and
Concrete rapidly curing linings that have little time to
wet out the surface.
In earlier work, the authors examined the in-
fluence of surface profile characteristics of
steel on coating and lining performance in im-
Fig. 8: Bonded geomembrane (polyurethane hybrid) to a concrete wall mersion. Failure to understand how the wet-
ting properties of the lining as well as the
adhesion forces can lead to serious repercussions for lining performance.22 In the case of 100%-
solids coatings that require heat for molecular mobility in order to facilitate mechanical and polar
adhesion, it is important to have a clean and well roughened substrate with a large number of reac-
tive sites.
The adhesion of organic coatings applied to steel surfaces is often described in terms of interfa-
cial hydrogen bonding between polar molecules, such as -OH and -COOH groups.2 It is reasonable
to postulate that the viscous polyurethane, polyurea, and hybrid linings cure so fast that they have
little time to (a) fully wet the steel surface or (b) develop the maximum number of hydrogen bonds
with the iron oxide-OH groups on the steel. Adhesion viewed in terms of Lewis acid-Lewis base the-
ory throws extra light on what is happening at the polymer-substrate interface.23,24 This theory is es-
pecially helpful regarding the wet adhesion characteristics of these linings when subjected to water
immersion. Acid-base theory envisages adhesion between acidic groups on abrasive-blasted steel
interacting with basic groups on the polymer. In essence, the greater the interaction is, the better
the adhesive bond will be. For instance, the basic groups on polyurethanes, polyureas, and their
hybrids are weak Lewis bases, and they form bonds with the iron oxide on carbon steel. These
weak bonds can readily be cleaved by water molecules when the coating is mechanically damaged
in immersion.
Hence, the real world observation is that several polyurethanes, polyureas, and hybrids may peel
to some extent away from carbon steel when damaged in immersed conditions. The authors are
currently investigating these adhesion phenomena on steel substrates in more detail.
In the protection of new and old concrete, many polyurethane and polyurethane hybrid linings
have demonstrated excellent service in a variety of municipal wastewater applications because
they can protect against microbiologically induced corrosion (MIC). Some polyurethane linings have
even been formulated with special anti-bacterial additives that are said to increase resistance
against MIC.25
Specialty polyurea linings can also provide very good protection to concrete in corrosive environ-
ments. For instance, spray applications of polyureas have been carried out inside neutralization
ponds in cogeneration facilities. Often, an epoxy primer is used to aid adhesion to the concrete fol-

17
lowed by one coat of polyurea.26 The asset can be rapidly returned to service because of the rapid
curing characteristics of the polyurea.
An innovative bonded geomembrane system for the application of certain polyurethane hybrids
to concrete surfaces has gained acceptance and is schematically depicted in Fig. 8. The geomem-
brane basically consists of pre-cut, heat-set, non-woven 100% polypropylene geotextile fabric pan-
els that are embedded between two layers of polyurethane hybrid.8 The panels are pressed onto a
still-fluid basecoat (or the concrete) and are held in place with Hilti-studs. Then, the panels are top-
coated. The system is especially suited to vertical, new, or old poured-in-place concrete surfaces
(walls). The polyurethane hybrid is reported to bridge bugholes and other voids in concrete as well
as eliminate pinholes produced by the normal outgassing of concrete. Hence, the fabric filters and
dissipates air or water vapor throughout itself. Therefore, there is said to be no way for outgassed
air to blow holes through the coating when it is being applied as a topcoat onto the geotextile fabric.
Once applied, (a) the embedded fabric can dissipate hydrostatic pressure and (b) remain unaf-
fected by normal surface shrinkage cracks, most dynamic cracks and the designed movement of
expansion joints in concrete.
Conclusions
Solvent-free polyurethanes, polyureas, and polyurethane/polyurea hybrid technologies have shown
promise for immersion service in various market segments.
A wide array of solvent-free technologies of this type can be formulated to have a plethora of
chemical physical properties by carefully selecting the amines, polyols, or a combination thereof.
This is particularly true for the polyurethanes and polyurethane hybrids.
Solvent-free polyurethanes, polyureas, and polyurethane/polyurea hybrid technologies can be
used in either a pure form or when slightly modified to customize required performance properties.
Acknowledgements
The authors are indebted to Dan Schneider of Polibrid, Jeff and Mark Buratto of Lifelast Inc., and
Mark Dromgool of KTA-Tator Australia for their valuable insight with respect to polyurethane,
polyurea, and polyurethane hybrid linings.
References
1. H. Hower, PolyureasWhats in a Name? JPCL (December 2003), pp. 3133.
2. C.H. Hare, Polyurethanes. In Protective Coatings, Fundamentals of Chemistry and Composition,
1994.
3. T. Kenworthy, 100% Solids Polyurethane and Polyurea: A Comparison of Properties and Uses,
JPCL (May 2003), pp. 5863.
4. R. Alliston and J. Dzatko, Recent Advances in Epoxy Coatings for Automated External
Rehabilitation of Pipelines, NACE Northern Area Western Region Conference, Anchorage, AK,
2001.
5. D.J. Primeaux II, Polyurea Elastomer Technology: History, Chemistry and Basic Formulating
Techniques, 2004.
6. D.J. Primeaux II, Two Component Polyurea Coatings/Linings. In Selecting Coatings for Industrial
and Marine Structures, SSPC: The Society for Protective Coatings, Pittsburgh, PA, 2008,
pp. 107123.
7. D.J. Primeaux II, The Protective Coatings Specialist and Polyurea: The Sequence of Events, JPCL
(September 2012), pp. 5057.
8. D. Schneider, Polibrid Coatings Inc., personal communication, August 2012.
9. M. Winter, Discussion on Polyurea Linings for Oilfield Applications, International Paint LLC, April

18
2011.
10. Introduction to Thick-Film Polyurethanes, Polyureas and Blends, T-6A-67 Technical Committee
Report No. 6A198, NACE International, Houston, TX, 1998, pp. 18.
11. M. Broekaert, Polyurea Spray Coatings: The Technology and Latest Developments, European
Coatings Conference, pp. 3755.
12. Polyurea Elastomeric Coating/Lining Systems, Polyurea Development Association General
Guidelines, Kansas City, MO, 2003.
13. G. Oertel, Polyurethane Handbook, Second Edition, Hanser Publishers, 1994.
14. M. Buratto, Lifelast Inc., personal communication, August 2012.
15. S. Guan, High Solids and 100 Percent Solids Aliphatic Polyurethanes for Exterior Applications: A
Survey of Approaches, JPCL (July 1997), pp. 4452.
16. D.J. Primeaux II, Spray Application of 100% Solids Plural-Component Aliphatic Polyurea
Elastomer Systems, JPCL (March 2001), pp. 2632.
17. R.D. Stutsman, Innovations in Penstock Lining, Hydro Review, May 1993.
18. Study on Hull Corrosion and Coatings, B.H. Levelton & Associates Ltd., October 1988.
19. R. Garret, HDIM, personal communication, November 2012.
20. M. ODonoghue, V.J. Datta, M. Winter, and C. Reed, Hubble, Bubble, Tests, and Trouble: The
Dark Side of Misreading the Relevance of Coating Testing, JPCL (May 2010), pp. 3045.
21. J. Buratto, Lifelast Inc., personal communication, October 2012.
22. M. ODonoghue, V.J.Datta , and R. Spotten, Angels and Demons in the Realm of Protective
Coatings: The Underworld of VOCs, JPCL (April 2011), pp. 1429.
23. F.M. Fowkes, The Role of Adhesion in Corrosion Protection by Organic Coatings, JOCCA
(October 1985), p. 229.
24. C. Reed, International Paint LLC, personal communication, October 2012. 25.
25. Madison Chemical, http://www.madisonchemical.com.
26. J. Wynne Darden, D. Zabinski, and S. Smith, Spray Polyurea Coatings for Protecting Concrete
Structures, pp. 178184.
27. L. Hanson, Hanson Group, personal communication, November 2012.
28. K. Nollsch, International Paint LLC, personal communication, November 2012. JPCL
Mike ODonoghue, Ph.D., Vijay Datta, MS, is the Di-

is the Director of Engi- rector of Industrial Mainte-
neering and Technical nance for International
Services for International Paint LLC, USA. He has
Paint LLC, Canada. He more than 40 years of ex-
has more than 30 years of perience in the marine and
experience in the protec- protective coatings industry.
tive coatings industry.
JPCL

Paint &
Coatings 19
Paint & Coatings

JPCL
By Brian Goldie
Where Are We Now?
A s with other topics in this special section, coatings developments have been covered in
JPCL regularly since 1985. The last main review was in the 25th Anniversary issue (Au-
gust 2009), where Michael Donkin summed up the changes in coating formulation for the
heavy-duty protective market since JPCL started. He discussed the drivers for change over that time
and how they had led to the introduction of new technologies. The present article will summarize
Donkins findings and then look at key developments for the protective and marine coatings since
2009. This article is not claimed to be comprehensive, but is instead a guide to some of the main con-
tinuing trends and innovations.
The 25-Year Review

Donkins August 2009 article discussed changes in coatings formulation over 25 years and the key
drivers for change. Drivers included increasing levels of legislation relating to protection of the environ-
ment from air pollution by reducing the emissions of volatile organic compounds (VOCs) from coatings,
and the need to reduce the use of raw materials that can pose risks to worker health and safety and to
the environment. In addition, there were higher customer expectations of performance and the need to
increase the lifetime of assets while reducing life cycle costs.
In the 1980s, there were very few VOC regulations for coatings, but by the 1990s, a revision of the
U.S. Clean Air Act resulted in national VOC rules, which have been getting stricter. There are also re-
gional, state, and local VOC regulations in the U.S. In Europe, the EU solvent emissions directive was
issued in 1999, but it wasnt until 2005 that the first restrictions on release of VOCs started to apply.
These regulations meant the virtual end of thermoplastic coatings (vinyls and chlorinated rubbers) be-
cause their very high VOC levels would never meet the regulations. Two-pack materials such as epox-
ies and polyurethanes became the resins of choice, but it was (and still is) a challenge for formulators
istockphoto.com/mstroz to maintain the high performance obtainable with these systems while reducing the level of solvent

20
used and the resultant VOC emissions. Increas-

ing the volume solids of the coating would re-
duce the VOC content, but this is not easy to do
without affecting application, drying, and other
properties of the coating, particularly if very high
solids levels are needed. Alternative resins and
curing agents are needed to achieve these very
high solids and/or more sophisticated application
equipment to apply them due to high viscosities.
An alternative technology was waterborne coat-
ings, which could be formulated with very low
VOC levels. Going back 25 years, waterborne
technology was limited to single-pack emulsions,
principally for interior use and typically not suit-
able for heavy-duty because of slow drying, poor
film properties, and adhesion when applied in
istockphoto.com/dbvirago
the field. Donkin did point out that over 25 years, two-component waterborne systems, such as epoxies
and polyurethanes, have been developed with performances close to their solvent-borne counterparts .
Raw materials identified as harmful to operators and the environment in the 25-year review included
lead and hexavalent chromate pigments, coal tars, and some plasticizers for acrylic emulsions. Cur-
rently, lead anticorrosion pigments are not used; chromate anticorrosion pigments have very limited
use (mainly in etch primers) in the protective coatings area; and the use of APEO plasticizers (alkyl
phenolethoxylate) is very restricted. There were periodic concerns about health risks from iso-
cyanates in coatings, but, in general, the industry knows how to handle these risks safely. In Eu-
rope, the REACH regulations began causing an area of uncertainty among formulators about what
materials may disappear from the market because of toxicity, or, more probably, the cost effective-
ness of screening these materials, which are often produced (and used) in small quantities.
Key Changes Since 2009

The drivers for development identified in the August JPCLs 25-year review are still valid, so what major
coating developments have occurred since then?
High-Solids vs Waterborne Coatings

So far, there has not been a dominant technology to meet the current environmental regulations. A
good barometer of coating development is to look at the (new) raw materials being promoted at trade
shows. The European Coatings Show is the largest and most important exhibition for the paint industry.
At the 2011 event, the main trends were an increased emphasis on waterborne systems, rather than
high solids, as a means of meeting the VOC requirements, and more attention to smart, or functional,
coatings.
However, this trend has not yet transferred to the protective or marine maintenance coating markets,
where use of waterborne coatings is relatively low, still due mainly to film forming and drying problems
in the field, as well as higher costs compared to traditional solvent-borne coatings. As a means of re-
ducing VOCs, higher solids and solvent-free coatings have been making more inroads. This is due es-
sentially to developments in curing agent technology giving faster cure times, and, to a certain extent,
to improved application equipment with better control on component mixing ratios of these two-pack
systems.

21
Waterborne Coatings
The introduction of waterborne coatings has
been limited essentially to two market areas:
coatings for internal use or very low and now
moderate corrosivity areas, and sealants and
coatings for concrete.
As metal coatings, low-VOC, two-component
waterborne polyurethanes have been developed
as primers and direct-to-metal systems for com-
ponents for light industrial projects. For concrete
and masonry applications, acrylic systems are
popular as topcoat/sealers to give good weather
and chemical resistance.
Waterborne epoxies have also been devel-
oped as concrete coatings, particularly for coat-
ing moisture-sensitive concrete (flooring).
istockphoto.com/leofrancini Systems have been developed as sealers and primers that can also be applied over green concrete
and that have good adhesion without the need for a profile. Waterborne epoxy floor topcoats are also
available, including antistatic versions.
High-Solids Coatings
Conventional solvent-borne coatings have volume solids contents of around 5060%. High-solids
coatings can be divided into solvent-free systems (100% solids) and those solvent-borne systems
with higher solids than the traditional coatings. In this summary, high-solids coatings are defined as
those with volume solids greater than 70%.
100% Solids Coatings

Developments in solvent-free systems include pure aliphatic polyurea topcoats for increased UV pro-
tection and good gloss and color retention, and flexible polyurethane systems with good waterproofing
properties for concrete floors, particularly in multi-story car parks exposed to aggressive environmental
conditions.
However, the most common 100% solids systems have been based on epoxy technology. Good ad-
hesion to steel and concrete, together with improved chemical and abrasion resistance compared to
the traditional solids content coatings, can be achieved with these systems.
Higher-Solids Coatings
The higher-solids protective coatings are generally based on polysiloxane resins and polyureas. High-
gloss topcoats for steel, with good durability and corrosion protection as well as fast cure have been
developed based on modified polysiloxanes. An even more environmentally friendly type of system, an
isocyanate-free single-component acrylic-siloxane, features good abrasion and a low VOC.
Aliphatic polyurea and polyaspartic resin systems also feature fast cure and high gloss for concrete
floors and for medium corrosivity steelwork protection.
High-solids epoxies with a range of curing agents, including phenalkamines, are used for immersion
and atmospheric protection of steelwork and concrete floors.
Conventional Coatings
Although the trend is for higher-solids (or waterborne) coatings to meet the VOC regulations,
there have also been developments in the traditional solvent-borne coatings, although volume

22
solids have increased to nearer the 60-70%

level. Again, urethanes and epoxies dominate
the developments, with acrylic urethane fin-
ishes giving high durability protection to the
structural steel of bridges, storage tanks, and
other structures, and polyurethanes providing
heavy-duty concrete floor coatings. The ag-
gressive demands of the offshore industry are
being met with high-performance zinc-rich
epoxy and conventionally pigmented epoxy
primers.
Specialty Coatings
Intumescent Coatings
istockphoto.com/GBlakeley
Fire protection has become an important subject for many raw material suppliers, as observed at the
European coatings shows in 2011 and 2013, and for paint companies. For cellulosic fires, 120 minutes
of protection are being provided by one-component, solvent-borne, acrylic intumescent coatings, with
some systems that can be applied under shop conditions or onsite.
Marine Coatings
As with protective coatings, there have been changes in marine coating over the past 30 years. The
25-year review identified the key developments that had occurred up until 2009. These mainly in-
volved hull coatings, resulting in two alternative high-performance antifouling technologies: tin-free
polishing coatings (copper-containing), and low-energy, foul-release coatings (silicon and fluo-
ropolymers).
Since 2009, very little has occurred, but various paint manufacturers have been making incre-
mental changes to their products to establish differentiation among them and have been partnering
with third-parties in an attempt to develop a methodology for measuring and validating claims about
potential fuel savings.
However, a copper-free, high-performance antifouling has become available that is based on self-
polishing binder technology and is aimed specially at keeping underwater hulls clean from fouling
while vessels are stationary in seawater.
The other major concern in the shipbuilding industry has been the corrosion of seawater ballast
tanks and the establishment of the IMOs Performance Standard for Ballast tank coatings. The IMO
requirements were essentially copied for a regulation describing a performance standard for cargo
oil tanks. This regulation has provoked some concern about the testing of (new) coatings to meet
the standard.
Polysiloxanes, which are showing increased usage in the protective coatings sector, are also
starting to appear in marine coatings, with durable, aesthetic topcoats that are easy to clean and
maintain, thus saving on costs
The Future
What does the future hold for protective and marine coatings? Health & safety and environmental
regulations will still drive coatings development. It is most likely that the VOC restrictions will get
even more restrictive. We do not know what technologies will become more dominant: waterborne
or high-solids. Various industry forecasts predict strong growth in waterborne systems, and going
by the products exhibited this year at the European Coatings show, the resin suppliers are all active
in this area. However, when I talk to the formulating chemists in the protective coating manufactur-

23
ers, they all agree that for the next 10 to 20 years, 80% of the heavy-duty and marine coatings will
be solvent-borne, albeit with higher volume solids than currently.
The use of other toxic or hazardous raw materials will be banned and more environmentally sus-
tainable raw materials will become available.
With a great deal of research being carried out in nanotechnology for coatings, it is expected that
we will see new smart or functional coatings coming to the market. Already, we have had demon-
strations of what this technology can deliver, and market acceptance should follow once new formu-
lations have been demonstrated in the field and production methods have been scaled-up.
Brian Goldie, technical editor for JPCL, has worked with protective coatings for many years,
including in the oil industry.
JPCL

Polyurethane
Pipe Coatings 24
Improving Polyurethane Pipe Coatings

By Andreas aus der
Wieschen, Matthias for Harsh Conditions
Wintermantel, Todd
Williams and Ahren
Bayer MaterialScience AG
Olson
L iquid polyurethane (PU) coating systems are of growing importance in the field of external
coatings for oil and gas pipelines. Coating systems based on aromatic polyisocyanates
and pre-polymers are used for new pipeline construction and for maintenance work.
Major drivers for the use of polyurethane coatings in pipe applications are their favorable cure char-
acteristics combined with superior mechanical properties especially under harsh conditions. Solvent-
free, two-component polyurethane systems have been approved as suitable protective coatings
systems within the pipeline industry and have been used for new tubes (steel and ductile iron) and for
field joints.
Furthermore polyurethanes are of growing importance for the renovation of oil and gas pipelines in
the field due to their ability to cure at low temperatures and their exceptional mechanical properties.
iStockphoto/olegusk 2011-2015 Technology Publishing Co.

25
Application Properties
Solvent-free two-component PU coatings have
the ability to create an inherent thickener effect
during application. This effect avoids sagging on
vertical surfaces and allows the formation of high
film thicknesses applied in one coating layer.
Therefore PU systems can fulfill the postulated
requirements with dry film thicknesses of about a
minimum of 500 m up to 5,000 m and higher.
Curing Time and Reactivity

Standard polyurethane systems are touch-dry
after approximately 60 minutes at 20 C or ap-
proximately 100 minutes at 5 C. The time for
Fig. 1: Polyurethane pipe coating formulations can be adjusted for shop-applied
or field-applied applications. through drying can vary from approximately 50
All images courtesy of the authors unless otherwise noted. minutes to approximately four hours at 20 C.
The reactivity of a polyurethane system can be
controlled by incorporating suitable catalysts.
Figure 1 shows the potential versatility of PU
coatings, adjusting reactivity by means of four
different formulations. With formulation Nos. 2
and 3, approximately 90 percent of the end
hardness depicted as Shore D has been
reached after roughly four hours which makes
these coatings generally suitable for field appli-
cation. Furthermore two formulations (Nos. 1
and 4) provide Shore hardness of D50 and D60
after only five minutes which would make those
combinations generally suitable for plant appli-
cation.
Mechanical Properties
Fig. 2: High versatility for adjusting mechanical properties elongation and Shore hardness Most relevant technical parameters for oil and
gas pipeline coatings are related to mechanical
properties such as film hardness and flexibility along with adhesion, and resistance to chemicals
and solvents. Liquid polyurethane pipe coatings typically provide increased impact resistance at
higher Shore hardness than standard pipe-coating epoxy systems. High-impact resistance is bene-
ficial because the transport of coated pipes to the site and the laying procedure in the soil can dam-
age the coating. Flexibility is important because PU-coated tubes in the field must endure bending
and must withstand frost during winter in colder regions. High abrasion resistance of the coating is
advantageous for withstanding soil stress.
The physical strength of polyurethane systems allows them to withstand mechanical forces longer,
such as creep. These mechanical properties can be customized by varying the ratio of hard and soft
segments, molecular weight and the crosslinking density of the cured film. Therefore it is possible to
create different PU coatings with physical properties that can range from soft, plastic across elastic up
to hard, rigid and even brittle.
Figure 2 displays the potential versatility in adjustment of mechanical properties of polyurethane
coatings. It compares different polyurethane formulations in terms of flexibility measured as elonga-

26
tion at break, and hardness measured as Shore

D. It is possible to achieve different films by varying
elongation at break that ranges from roughly 5 per-
cent up to roughly 130 percent. The elongation at
break of standard polyurethane pipeline coatings
ranges in between 10 percent and 20 percent.
By combining polyurethane formulations which
provide different levels of hardness, it is possible to
create a coating system resembling a polyurea
system, with a hard primer plus an elastic layer; or
a three-layer system consisting of a hard primer
plus an adhesive plus an elastic polyethylene. As
shown in Figure 2, using PU1 (hard primer) as the
initial layer, PU4 as the intermediate coat and PU7
as the elastic finish coat, total film thickness of
1,000 m, 3,000 m, or even higher could be
achieved. The advantage of such a paint system is
its effective adhesion due to all components being
of the same technology, PU onto PU.
Fig. 3: Schematic design of the cathodic disbonding test
Development of Rigid, Two-Component Polyurethane Coatings

Market requirements led to development of rigid, two-component polyurethane coatings by improving
on already-established polyurethane raw materials. Desired attributes of this advanced coating in-
cluded serviceability for buried pipelines positioned above- and below-underground-water level, short-
drying time, short-curing time, single-coat suitability for direct-to-metal application, durability under
harsh conditions, favorable cathodic-disbonding properties, favorable impact properties and straight
mixing ratio.
Steps of development included screening of suitable building blocks; selection of the best candi-
dates for extended testing for anticorrosion properties, adhesion, porosity and curing characteristics;
working out start formulations for test coatings; working out straight mixing ratios and rheological pro-
file. The develpment outcome is a "rigid" or "strucutral" class of PU pipeline coatings based on new
polyols and polyisocyanate pre-polymers.
Laboratory Testing
Cathodic Disbonding Test
Various test procedures exist within the pipeline industry and have different requirements for voltage,
temperature, salt solution and test period. The most regularly-used test methods follow standards
ASTM G8, Standard Test Methods for Cathodic Disbonding of Pipeline Coatings, and ASTM G42,
Standard Test Method for Cathodic Disbonding of Pipeline Coatings Subjected to Elevated Tempera-
tures.
Polyurethane pipe coatings which provide higher crosslinking densities in the cured film usually pass
the cathodic disbonding tests up to 65 C. The prepared surface, specifically the roughness profile after
blasting, has an important influence on adhesion and cathodic-disbonding-test results. The minimum
surface quality should be Sa 2.5 with a roughness minimum of 5070 m, and a recommended rough-
ness of 80100 m.
Pipe coatings must fulfill certain cathodic-disbonding properties. Figure 3 illustrates a schematic de-
sign of a cathodic disbonding (CD) test. CD tests are used to evaluate the damaged coating's delami-

27
nation behavior using conditions that model the service environment including cathodic
protection, elevated service temperature, and salt solution (representing ground water).
Steel panels with different surface profiles (roughness) were tested at various tempera-
tures. Coated steel panels were sent to an independent test institute for investigation of
cathodic disbonding characteristics according to T/SP/CW/6 Part 1. The tests were car-
ried out for 15 days at 80 C and for 15 days at 95 C. The electrolyte was maintained at
30 C in both tests. The results of these tests were approximately 3 mm disbondment
after 15 days at 80 C and approximately 5 mm disbondment after 15 days at 95 C.
Figure 4 depicts the result of the cathodic disbonding test after 14 days at 80 C. The
result in terms of adhesion and disbondment is very good at surface roughness of ap-
proximately 30m. The requirement is normally 80120m. In this case it was not possi-
ble to lift the coating with a knife at the end of the test.
Fig. 4: Rigid polyurethane coating after cathodic-dis-

Film Hardness and Impact Test
bonding test for 14 days at 80 C
One development goal was to decrease the time involved in the en-
Table 1: Measurement of Shore Hardness Over Time tire maintenance process, thereby reducing the time until backfilling
Rigid Polyurethane Shore D Hardness @ RT of the coated pipe could take place. The Shore hardness formation is
After 1h 73 a good indicator of curing therefore measuring the hardness of the
applied film over time can provide an informative assessment of me-
After 3h 78
chanical performance (Table 1).
After 5h 78
After coated samples of a start formulation had been success-
After 7h 81
fully tested, two field trials were carried out. The field application was
After 9h 81
arranged in agreement with an oil and gas company in the Middle
After 24h 82
East. It was done to study and evaluate the new building blocks for
After 48h 82
rigid, two-component polyurethane coatings for external surfaces of
After 7 days 82 oil and gas pipelines under real conditions.
Blasting
After shot blasting the surface with garnet, the profile measured Sa 2.5 and the average
roughness was approximately 70 m.
Application of the Test Coating

Two layers of the test coating were applied wet on wet with roughly 10 minutes of curing time
in between the coats. Each layer was applied with 34 passes (Fig. 5). The pot life measured
three minutes and after about 30 minutes the coating was tack free.
The final inspection after application on-site showed that leveling and sag resistance was
Fig. 5: Application of test coating in

satisfactory. The dry-film thickness was measured with 1,6501,900 microns. As no blisters
the Middle East or failures were observed, backfilling of the pipe was done three hours after application.
Inspection of the Test Coating

After 15 months in wet soil with high salt content, the pipeline was excavated and the rigid
polyurethane test coating was inspected by experts from the participating oil and gas com-
pany. The coating was in excellent condition and did not show any damage, bubbles, rust or
delamination (Fig. 6, p 40). The oil and gas company representatives tried unsuccessfully to
cross-cut the coating by using a chisel.
Fig. 6: Inspection of rigid test coating after 15

months. No defects or damages were observed.

28
Table 2: Rough Comparison of Solvent-Free, Comparison of Existing Coatings

Two-Component Polyurethane Coatings This positive result prompted a comparison with existing sol-
Properties 1 2 3 4 vent-free, aromatic, two-component polyurethane coatings
also deemed suitable for pipelines above- and below-ground
Crosslinked Density very high high medium low water level and specific service temperatures (Table 2).
Mechanical Property rigid rigid-hard hard-flexible flexible-soft
Cathodic Disbonding* ++ + 0 -- Rigid Polyurethane Type 1
Elongation <10% 10% ~2030% >100% By roughly comparing four cases in consideration of the
Shore Hardness D75 ~D70 ~D60 <D30 crosslinking density of the cured film, the influence of the
Impact + ++ ++ ++ crosslinking network on the coating properties was apparent.
Bending Properties 0 ++ ++ ++ The cured film of rigid polyurethane type 1 is highly
Adhesion ++ ++ ++ ++
crosslinked yielding exceptional cathodic-disbonding proper-
*at high temperature (>80 C)

ties at temperatures of 8095 C.
Pipe coatings generally have acceptable impact resist-
ance of 8 J/mm at room temperature and Shore D hard-
Table 3: Requirements of EN 10289 (selection)
ness of 75 to 85. The rigid PU coating had a value of
Impact resistance 5 J x k x mm (23 C) mm of coating thickness
approximately 16 J/mm at Shore hardness of ca. D80. The
Adhesion test, pull-off method 7 MPa (23 C)
rigid PU coating's highly crosslinked density imparts much
Cathodic disbonding test Average 6 mm, max. 8 mm (28d at RT, 2d at 60 C)
lower water absorption than standard coatings and pro-
Elongation No requirement! vides improved anticorrosion properties. The elongation at
break is less than 10 percent which could yield less bend-
Table 4: New Polyols for Rigid Polyurethane Coatings ing ability for new coated tubes in the field during the con-
struction of a new pipeline, although it could be reasonable
Polyol Property Polyol 1 Polyol 2 Polyol 3 Polyol 4
to bend uncoated tubes first and then apply the coating.
OH content [wt. %] 12.1 14.2 16.7 18.8 This material is potentially suitable for harsh conditions
Viscosity [mPas] 5,500 5,400 1,800 19,200 like high-ground-water level covering the pipeline, and also
Density [g/cm3] 1.06 1.02 1.04 1.02 for higher service temperatures (>80 C). Backfilling with the
Average Functionality 3.7 4 3 4 test coating was done only three hours after application,
which is considerably less than the typical duration. Fur-
Table 5: New Polyisocyanate Pre-Polymers thermore, the test coating fulfills several requirements of the international epoxy
for Rigid Polyurethane Coatings standard EN 10289, "Steel tubes and fittings for onshore and offshore pipelines - Ex-
ternal liquid applied epoxy and epoxy-modified coatings" (Table 3).
Property Pre-Polymer Pre-Polymer 2
NCO content [wt. %] 21.5 24
Rigid Polyurethane Types 2, 3 and 4
Viscosity [mPas] 400 220
Coating types 2 and 3 are standard pipe-coating systems (also applicable for ductile
Density [g/cm3] 1.16 1.17
iron pipes), existing in the market for decades with proven performance. These coat-
ings are typically used for pipelines with service temperatures of up to 60 C and higher depending on
the formulation. As type 3 is a relatively hard coating, it might be a better option for colder regions with
permanent frost because its increased flexibility could help prevent cracking and coating failure.
Type 4, an elastomeric, might be not a good contender as direct-to-metal pipe coating, especially at
high service temperatures because the crosslinking density is low compared to the others, which has a
direct negative impact on its corrosion protection and cathodic-disbonding properties.
New Raw Materials for Rigid Polyurethane

By combining the polyols shown in Table 4 with the polyisocyanate pre-polymers shown in Table 5 it is
possible to achieve exceptional anticorrosion properties. The combination of polyol 1 and pre-polymer
1 was tested in the field under real conditions. In addition, it is possible to achieve mixing ratios of 1:1
and 2:1 by volume.

29
Conclusion
Polyurethane pipe coatings are a versatile product class that can be tailored to meet a wide range of
end-use applications. Varying the catalyst, crosslinker and polyol allows the coating formulator to de-
velop a range of properties from elastomeric to rigid. A new class of rigid polyurethane pipe coating raw
materials were developed to meet higher cathodic disbondment requirements and their performance
under harsh, real-world conditions looks promising.
About the Authors

Andreas aus der Wieschen studied chemistry with a focus on paints and coatings at the University of
Applied Sciences, Krefeld. He joined Bayer AG in 1998 and has overseen the companys market de-
velopment of polyurethane raw materials for pipeline coatings since 2009.
Dr. Matthias Wintermantel holds a Ph.D. in macromolecular chemistry from the University of Bayreuth,
Germany. Since October of 2012 Dr. Wintermantel has been responsible for product development for
protective coatings, construction coatings and pipe coatings within the EMEA region and Latin America
for Bayer MaterialScience AG.
Todd Williams earned a Ph.D. from the University of Southern Mississippi in 2005 where he wrote his
thesis on alkyd-modified latexes. After a two-year post-doctoral position studying polyurethane coatings
and two years with startup Segetis focusing on renewable polymers, Williams joined Bayer Materi-
alScience developing UV-curable coating formulations. In 2012 he became manager of the companys
corrosion protection group.
Ahren Olson is the marketing manager for corrosion protection with Bayer MaterialScience LLC in
Pittsburgh, Pa. He has been with Bayer for 10 years, with experience in automotive, construction and
corrosion-protection coatings. He holds a Bachelor of Arts degree with a major in chemistry from The
College of Wooster. Mr. Olson currently provides market development support in Bayers efforts to un-
derstand and prevent corrosion for the heavy and light-duty industrial-maintenance markets.
JPCL

Raw Materials
Suppliers 30
Raw Material Suppliers Answer

By Brian Goldie,
JPCL Calls for Green and Smart Coatings
A t the end of March 2011, the worlds paint raw material suppliers met at the European
Coatings Show in Nuremberg, Germany.
The bienniel show, which is the largest coatings event in Europe, had a record 26,000
trade visitors this year. Some 890 suppliers to the paint industry from 45 countries displayed their new
and traditional products. At the parallel European Coatings Congress, 650 participants from 40 coun-
tries heard some 150 papers of outstanding interest in the topical issues of this highly innovative sec-
tor.
This review of the exhibition and conference discusses what the developments in new products
and technologies mean to users of protective coatings and what users can expect in new paints or im-
proved performance. The properties described in the review are based on comments and data sheets
from suppliers and have not been independently verified.
Photo courtesy of NuernbergMesse and Thomas Geiger 2011-2015 Technology Publishing Co.
31
Trends: Green, Waterborne, and Smart

Most new products from coating raw material suppliers at
the show are based on ingredients from renewable or sus-
tainable resources. The concept of green products, even
the color theme, was carried over in a number of stand
designs.
The reliance on fossil fuels as sources of raw materials
for coatings is shifting to a reliance on natural products,
with suppliers also being sensitive to the need to not affect
the use of these materials in the human food chain. For
example, suppliers that incorporate soya-based ingredi-
ents into their raw materials are aware of the effects on
the supply of soya ingredients because they are a major
source of nutrition for many countries.
Although new products for high-solids are still in demand,
an underlying trend at the show was an increasing empha-
sis on waterborne systems rather than high(er) solids as a
means of meeting the more stringent regulations on volatile
organic compound (VOC) content in coatings.
A third trend was an increasing number of smart, or
functional, coatings developments on display.
Approximately 150 papers were presented
during the European Coatings Congress.
Photos courtesy of NuernbergMesse.
Resins and Curing Agents
The major raw material suppliersBASF, Bayer, and Dowall exhibited their comprehensive prod-
uct ranges for a wide variety of industries.
The industrial coatings market is one of the most diverse that BASF serves, and it introduced two
more products.
Basonat LR 9080, a waterborne, fast-drying polyisocyanate mainly for general industrial coatings,
allows faster handling of the coated substrate.
Acronal PRO 80, a modified acrylic dispersion for metal primers, not only offers high-performance
corrosion protection but it also is free of alkylphenol ethoxylates (APEO).
APEOs are non-ionic surfactants with an emulsifying and dispersing action that makes them suitable
for a very large variety of applications; however, APEOs, especially nonyl phenol ethoxylates, are
considered very toxic for aquatic life and, in Europe, are no longer allowed or wanted.
Polyurethane coatings formulated with Bayer raw materials are already found in a wide range of ap-
plications; however, the companys latest developments go even further as coatings increasingly take
on new functions. Bayers and other suppliers new polyurethane products and developments will be
detailed in the next issue of JPCL.
The Dow Chemical Companys five businesses combined to demonstrate the benefits of the com-
panys latest technological advances in their industries. Dow Construction Chemicals introduced white
reflective roof coatings, a new technology to reduce over-heating in buildings. At the top of most agen-
das in todays building industry is the drive to create products that are more sustainable and take
maximum advantage of ways to save energy. To this end, one of the main areas promising significant
progress is roof technology, specifically, the development of coatings aimed at lowering building tem-
peratures caused by radiant sunlight.
After many years of study into the indoor temperature effects of direct sunlight, Dow Construction
Chemicals developed and, at the show, highlighted its latest innovations in its cool roof technology

32
program: reflective elastomeric coatings that are durable

and efficient, with the potential of making the single largest
contribution to reducing CO2 emissions from domestic,
commercial, and industrial buildings. In addition, the cool
roof coatings are designed to play a significant role in ex-
tending the longevity of structural roofing materials.
Another company promoting cool roofing was Arkema.
It showcased its polyvinylidene fluoride (PVDF) resins for
long-life coatings dedicated to cool roofing. The company
also featured its very low VOC acrylic emulsions.
The Huntsman Performance Products division brought
two new fast cycloaliphatic amine-curing agents to the
market. XTA-801 and DCH-99, which offer low viscosity,
low color, and high reactivity, are designed for use in coat-
ings, flooring, and other applications. When combined
with the companys Jeffamine polyetheramine (PEA)
hardeners, the new curing agents can enhance glass tran-
sition temperatures, modulus, and hardness, and can im-
prove chemical resistance as well as low temperature
A record 26,000 people attended the exhibition. curing properties. The company also introduced a PEA
epoxy curing agent that offers low viscosity, low color, higher glass transition temperatures, and faster
property development than other solutions typically available. Another new product from Huntsman is
a cycloaliphatic amine chain extender for polyurea spray. The extender is designed to be easy to use
and environmentally friendly.
From Wacker came product innovations and customized solutions for industrial coatings, con-
struction, and adhesives and sealants. It also unveiled SILRES IC 368, a liquid, solventless silicone
resin intermediate for highly weatherable coatings. The new silicone resin is formulated so that an ad-
dition of just 15% increases the UV resistance and weatherability of the organic binder in the coating
system without impairing the mechanical properties of the system.
Lab and open-air weathering tests show that SILRES IC 368 confers much better gloss retention,
superior weatherability, better heat resistance, and a longer service life compared to similar products.
Designed to be highly versatile, the new intermediate is suitable for modifying alkyd resins, hydroxy-
functional acrylic resins, and hydroxy-functional polyesters commonly used in industrial coatings for
metal, including coil coating.
Perstorp Holding ABs Voxtar is, according to the company, the worlds only renewable pen-
taerythritol platform. Voxtar cuts a carbon footprint by up to 75% compared to that of conventional
fossil-based penta and di-penta polyols while providing identical properties and performance. It is
made from bio-based acetic aldehyde and formaldehyde. Combining the renewability of Voxtar with
the latest waterborne technology significantly shrinks the carbon footprint of high-solid alkyd paints and
alkyd emulsion paints compared to traditional petroleum-based latex paints.
The product also exemplifies the companys efforts to reduce emissions and energy consumption
associated with raw material manufacturingPerstorp uses renewable raw materials such as bio
methanol to decrease the use of petrochemical raw materials. Moreover, renewable energy has been
powering parts of the companys production sites since 1991, and more than 80% of its R&D work is
focused on environmental innovation.
Perstorps approach to innovation is driven by sustainability on three fronts: reducing emissions
and energy consumption in raw material manufacturing; developing products that enable customers

33
to formulate low-environmental impact solutions; and

high-performance additives that enable more durable and
long-lasting end products.
Omnova Solutions, together with its recently acquired
Eliokem, is a significant supplier of styrene butadiene lat-
tices, acrylic emulsions, bio-based polymers, and addi-
tives. The company presented a new range of
hydrophobic acrylic emulsions under the Omnapel
name. The emulsions exhibit exceptional water resist-
ance, good exterior durability, and other resistance prop-
erties, making them useful in water-resistant coatings
such as concrete sealers. In addition, they can be
blended with other polymer systems to enhance water re-
sistance and durability. Some of the products can be used
to create coatings that, when cured above 135 C, are in-
soluble to acids, alkalis, and organic solvents.
Incorez introduced a waterborne epoxy curing agentIn-
corez 148/604 to help companies comply with the re-
quirements of the VOC Solvents Emissions Directive, the
Industry professionals check out new products from suppliers.

European Unions main policy instrument for reducing in-
dustrial emissions of VOCs.
Charles Lynch, Commercial Manager at Incorez, commented on the launch: Our new waterborne
epoxy curing agent is a water soluble polyamine curing agent that is APEO, formaldehyde and solvent
free, and so does not contribute to the VOC levels of the coating formulation. It is designed to produce
very tough and durable, high-gloss waterbased coatings with both liquid and solid epoxy resins. In par-
ticular, this hardener displays very good compatibility with neat Bisphenol A type liquid epoxies, such as
Epikote 828, to provide excellent hardness and cure development.
Croda Coatings & Polymers brought out its latest green innovation, Priamine 1071, for marine
and protective coatings. Priamine 1071 is a low viscosity curing agent for epoxy systems. It can be
used as a main curative and co-hardener, and it addresses a growing demand for the development
of high-solids, low-VOC formulations. Due to its high flexibility and chemical resistance, this novel
dimer diamine, bio-based building block is suitable for interior and exterior coating applications that
require durability under severe conditions. Its sealant and protective properties as well as its improved
adhesion properties can extend the service life of a coating.
Air Products featured its next generation of epoxy curing agents aimed at helping formulators de-
sign coatings solutions that benefit the environment and that are effective over a range of coating ap-
plications. Using its Total Reactive Technology approach, the company developed a modified
polyamine curing agent that is 100% reactive (to epoxy resins) and that eliminates the need for a
plasticizer. With its high performance and fast curing at ambient and low temperatures, the techno-
logy has already been successfully used for indoor flooring applications. The plasticizer-free techno-
logy is also more sustainable and has near negligible emissions throughout the lifetime of the coating.
According to experts at Air Products, the new generation technology complements the increasing pop-
ularity of water-based systems.
Additives
Green again was the word when it came to new additives, but, as stressed by Byk Chemie, no
global standard precisely defines green in the context of the surface coating industry. Every-one has

34
a perception of its meaning, and the demand for green products keeps growing, hence the number
of new developments. Green is also a synonym for environmentally friendly, but what does that
phrase mean? According to Byk, the VOC content of products and raw materials is one important in-
dicator of their impact on the environment; however, the deciding factors are often the various eco-
labeling systems in existence and the percentage of renewable materials in a product. Formulators
often have to balance the use and type of green materials against performance requirements. With
this in mind, Byk has developed products and technologies that meet current environmental stan-
dards without sacrificing the quality of the products being replaced.
New products on show included Byk-1740, a green defoamer based on eco-friendly and sustain-
able raw materialsvegetable oil derivatives. It is VOC-free and completely sustainable while pro-
viding the same performance as the standard mineral oil-based defoamers. Especially suitable for
waterborne emulsion paints, the new defoamer has no negative influence on color or odor.
Other new Byk products exhibited for waterborne systems included silicone-free defoamers, de-
foamers free of mineral oil as well as silicone, and wetting and dispersing agents.
According to Clariant, it was one of the first companies to offer a 100% APEO-free alternative for
manufacturing binder emulsion polymers. In addition to its low VOC levels, Emulsogen EPA 073 is
now one of few anionic emulsifiers with FDA approval. When combined with nonionic emulsifiers like
Emulsogen LCN 287 or Emulsogen LCN 407, these APEO-free emulsifiers offer increased latex sta-
bility and better shelf life. They increase the availability of more environmentally acceptable alterna-
tives to solvent-borne paints and coatings in contact with foodstuffs.
Rhodia is also moving toward more sustainable coatings with its portfolio of breakthrough per-
formance additives created to meet formulators demands for specific solutions for creating the next
generation of eco-friendly coatings. The company highlighted its new eco-friendly evaluation ap-
proach to designing sustainable coatings by spotlighting its growing line of zero-VOC, APEO-free
performance additives and solvents for waterborne coating. Rhodoline OTE is a novel zero-VOC,
APEO-free range of additives for extended open time (workability) in waterborne coating formula-
tions. It provides a two- to four-fold increase in open time without the addition of solvents, thus giv-
ing painters longer to work overlays seamlessly or to touch up paint to correct imperfections such as
drips and brush marks.
Air Products launched a new range of defoamers and de-aerators based on organic, silicone, and
molecular chemistry that will allow manufacturers to produce high-performance coatings that are
more durable, efficient, and environmentally friendly. The defoamers and de-aerators are particularly
useful for waterborne systems and can be used in floor coatings in combination with the companys
epoxy curing agent technology.
BASF also featured Dehydran SE 2, a high-performance silicone polymer emulsion defoamer for
premium waterborne paints and clear coats. It offers good foam suppression and long-term persis-
tency, is highly compatible and easy to handle, and minimizes gloss reduction. Because Dehydran
SE 2 is VOC-free and has an ultra-low semi-volatile organic compound (SVOC) content, it also helps
manufacturers formulate paints and clear coats that meet the requirements of environmental stan-
dards and safety certifications, such as the German TV, Green Seal GS-11, the EU Ecolabel, and
the Blue Angel.
In the range of rheology modifiers, BASF introduced DSX 3801, a VOC-free, mid-shear rheology
modifier with excellent ICI thickening. The ICI build of the thickener clearly exceeds that of benchmark
waterborne products, even at lower dosages. Due to the high efficiency and improved performance
of DSX 3801, a smaller amount of it is needed in formulationsa do more with less approach that
delivers sustainability benefits.
Dow Coating Materials announced the launch of its new EVOQUE Pre-Composite Polymer Tech-

35
nologya revolutionary development for paints and coatings that promises to change the way for-
mulators think about hiding and the use of titanium dioxide (TiO2). The acrylic-based technology im-
proves the particle distribution and light scattering efficiency of TiO2, facilitating improvements in
hiding efficiency and allowing for up to 20 percent less TiO2 used in the formulation. Additional ben-
efits include improved barrier properties such as stain and corrosion resistance.
Depending on their formulation goals, paint manufacturers can choose to reduce TiO2 content or
improve hiding while they improve paint performance. The Pre-Composite Polymer Technology may
also help formulators reduce the carbon footprint of their end products by reducing the energy foot-
print that comes from mining, processing, and transporting TiO2 to their formulation plants. Dow Coat-
ing Materials is conducting a life cycle analysis, which will be verified by a third party, to quantify the
full spectrum of sustainability advantages that may result from using its new technology.
Pigments
The trend for green products also extended into the new pigments offered from the various suppli-
ers. The developments were predominately in color pigments, although some new environmentally
friendly anti-corrosion pigments were on show from companies such as Halox, Nubiola, SNCZ,
Sachtleben, and Pigmentan.
Smart Coatings
One class of smart coatings are the self-healing systems that incorporate Bayer MaterialScience
products. The systems are functionalized anti-corrosion coatings or topcoats that can heal dam-
age autonomously, similar to the self-healing mechanism of the human skin.
Other products for smart coatings were for graffiti resistance.
New perspectives for smart coatings are being found in marine coatings with the use of carbon
nanotubes, again from Bayer MaterialScience. The nanotubes allow another approach to provid-
ing different properties and additional functions, and their use as coating additives could open up
even more intriguing perspectives. The high mechanical strength and electrical conductivity of
the particles, in particular, promise novel possibilities for formulating coatings and for improving
the strength of structural components while keeping their weight extremely low. Novel epoxy-gel
coatings with nanotubes are already significantly improving the scratch-resistance of coatings for
ship hulls.
Nanotechnology is also being used to give floor coatings with improved properties. The COL.9
nano-based binder from BASF, which has been used to produce self-cleaning wall coatings, can
also be used to coat substrates such as concrete, stone, or tiles. This means that, for example, tire
marks or oil stains on garage floors can be a thing of the past. The functional principle is the same
for both facade and floor applications. The binder combines the benefits of synthetic resin disper-
sions with those of silicates. (COL.9 is a dispersion of organic polymer particles in which nanoscale
particles of silica are incorporated.)
The organic part of the binder, i.e., the acrylic resin, ensures sufficient elasticity while the mineral
part lends the colored coating the required rigidity. This makes coatings particularly resilient as well
as resistant to dirt and chemicals.
Congress
The themes at the show were also prominent at the parallel. In fact, the plenary lecture by Professor
Matthias Beller, University of Rostock, Germany, was Sustainable chemistry: A key technology for the
21st century, which addressed the improvement of industrial chemicals production. Approximately
Dr. Matthias Beller addressed sustainable
150 papers were presented in 25 sessions covering a range of technologies and end uses, with specific
chemistry in his keynote speech.

36
sessions on sustainability and bio-based coatings, smart coatings, and nano-technology. The majority
of new products on show were also the subject of detailed technical presentations.
Summary
The emphasis of the products being exhibited and technologies presented was on their environmen-
tally friendliness, with materials for waterborne systems predominating. Companies were also keen
to explain their desire to use renewable ingredients as their raw material sources and their efforts in
reducing the carbon footprint of their production facilities.
Brian Goldie, technical editor for JPCL, has worked with protective coatings for many years,
including in the oil industry.
JPCL

CorrosionControlEbook

Enviado por

Dados do documento

Título original

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

CorrosionControlEbook

Enviado por

Direitos autorais:

Formatos disponíveis

ADVANCES IN

Copyright 2011 - 2015 by

All Rights Reserved

This eBook may not be copied or redistributed

2011-2015 Technology Publishing Co.

Titans of the Abyss: Polyurethane, Polyurea, and Hybrid Lining

30 Brian Goldie, JPCL

2011-2015 Technology Publishing Co.

2011-2015 Technology Publishing Co.

FEVE Technology for

Fig. 1: The Swan Bridge in Muroran,

2011-2015 Technology Publishing Co.

local municipalities and the private sector

FEVE Resin Structure

Coating Formulations with FEVE Resins

2011-2015 Technology Publishing Co.

vents have preserved the presence of this

2011-2015 Technology Publishing Co.

2011-2015 Technology Publishing Co.

About the Author

2011-2015 Technology Publishing Co.

Titans of the Abyss:

istockphoto.com/whitphotography 2011-2015 Technology Publishing Co.

Lining Selection: The Influence of Chemistry in Polyurethane, Polyurea, and Hybrids

Case History: Paper Mill Wastewater Treatment Clarifier, U.S.

2011-2015 Technology Publishing Co.

As expected by the term hybrid, in the film formation of a hybrid lining,

2011-2015 Technology Publishing Co.

Table 1: Reactions of the Isocyanate Group2 Hybrid: For reference purposes, a

Imino groups - NH Sulfonamide groups - SO2NH2

2011-2015 Technology Publishing Co.

Polyurethane lining in paper mill wastewater treatment

cross linked film (NCO:OH >1) will yield a

2011-2015 Technology Publishing Co.

polyurethanes are used for immersion service.

Polyureas: Film Formation

Advantages of Polyurea Linings As with solvent-free polyurethane linings, in the

2011-2015 Technology Publishing Co.

Advantages of Hybrid Linings coating is difficult. Some manufacturers make

Polyurethane hybrid lining on steel internals of penstock8

Hybrids: Film Formation

2011-2015 Technology Publishing Co.

Case History: Penstock Internals, Australia

Case History: Wastewater Treatment Clarifier, U.S.

ASTM E96, Method B.

2011-2015 Technology Publishing Co.

2011-2015 Technology Publishing Co.

2011-2015 Technology Publishing Co.

and polyurethane hybrid) coating based on ra-

2011-2015 Technology Publishing Co.

2011-2015 Technology Publishing Co.

Mike ODonoghue, Ph.D., Vijay Datta, MS, is the Di-

2011-2015 Technology Publishing Co.

Paint & Coatings

The 25-Year Review

2011-2015 Technology Publishing Co.

used and the resultant VOC emissions. Increas-

Key Changes Since 2009

High-Solids vs Waterborne Coatings

2011-2015 Technology Publishing Co.

100% Solids Coatings

2011-2015 Technology Publishing Co.

solids have increased to nearer the 60-70%